Nickel pi-allyl halogenoacetates,their use as catalysts for the stereospecific polymerization of unsaturated organic compound

ABSTRACT

A process for stereospecific polymerization of conjugated diolefins with a catalyst which is the reaction product of allyl halogenoacetate and nickel carbonyl or nickel olefin complex.

United States Patent 1191 1111 3,719,653

Dawans March 6, 1973 [54] NICKEL 7T-ALLYL [52] U.S. Cl ..260/94.3, 260/82.1 HALOGENOACETATES, THEIR USE AS [5 l] Int. Cl ..C08d 1/14, C08d 3/06, C08b 3/08 CATALYSTS FOR THE [58] Field of Search, ..260/94.3 STEREOSPECIFIC POLYMERIZATION OF UNSATURATED ORGANIC [561 References CM COMPOUND UNITED STATES PATENTS [75] Invent": Francois Dawans 78 BOugival 3,379,706 8/1968 Wilke ..260/94.3 France 3,468,866 9/1969 Alferou et al. .....260/94.3 Y 3,501,415 3/1970 Herwig et a]. ..252/429 [73] Asslgnee' 2323:5315:' gl xg m 3,510,466 5/1970 Lugli et a1. ..260/94.3 3,542,695 11/1970 Dawans et a1. ..252/431 Malma1son, France [22] Filed: July 23, 1970 Primary Examiner-James A. Seidleck Assistant Examiner-William F. l-lamrock [21] Appl 63983 Attorney-Craig, Antonelli, Stewart & Hill Related U.S. Application Data [57] ABSTRACT [62] Division of Ser. No. 753,769, Aug. 12, 1968, Pat. No.

3,660,445 A process for stereospec1fic polymerizatlon of COD]!!- gated diolefins with a catalyst which is the reaction 3 Foreign Application p i Data product of allyl halogenoacetate and nickel carbonyl Aug. 23, 1967 France ..67118816 or nickel olefin complex.

1 1 Claims, No Drawings NICKEL 1r-ALLYL HALOGENOACETATES, THEIR USE'AS CATALYSTS FOR THE STEREOSPECIFIC POLYMERIZATION OF UNSATURATED ORGANIC COMPOUND This is a division of application Ser. No. 753,769, filed Aug. 12, 1968 now U.S. Pat. No. 3,660,445.

This invention relates to the preparation and use of a new catalytic system providing for the conversion of monomeric compounds with ethylenic bonds to polymers of high molecular weight. More particularly this process is convenient for conversion of butadiene to apolymer whose microstructure essentially exhibits cis-1,4 i.e. in most cases for at least 95 percent of the constitutive units, and whose intrinsic viscosity, measured in toluene, at 30C, may be higher than ldl/g.

It is known that the compounds of the transition metals of the X Me 1r allyl type, wherein Me is a transition metal from the 4th to 8th sub-groups of the periodical classification of elements, and X is a halogen, are catalysts for polymerization of olefins or diolefins but, in most cases, they require the combined use of additives such as Lewis acids or bases so as to produce, with satisfactory activity and selectivity for industrial use, stereoregular polymers of high molecular weight.

It has now been discovered that nickel 1r -allyl halogenoacetates derivatives exhibit, unexpectedly, a catalytic activity in polymerization, whereby can be obtained, in the absence of any additive and even under atmospheric pressure and at a temperature close to the ambient temperature, highly stereoregular polymers and more particularly cis-l,4 polybutadiene exhibiting a series of properties which make them of advantageous use in the field of synthetic elastomers.

The catalysts according to this invention comply with the general formula wherein X represents a halogen, preferably fluor, n being an integer selected from the values I, 2 or 3 and preferably equal to 3; R,,R R,, R and R which may be identical to or different from each other, represent a hydrogen atom or alkyl, cycloalkyl', aralkyl or aryl radicals, the groups or radicals R 11,, R, and R being optionally combined at least by two in a cyclic system, preferably comprising from five to 12 terms, m being an integer often equal to 1 or 2.

These compounds offer numerous advantages they are easily produced according to the process ofthis invention, they have a good stability in time to the ambient temperature under inert atmosphere, which makes easier their storage and handling. Moreover they exhibit a high activity and selectivity in the process of polymerizing conjugated diolefins; specially in the case of butadiene they give rise to high polymers with high contents in cis-l,4 units, free from gel and whose molecular weights are distributed within a narrow range.

The nickel 'rr-allyl halogenoacetate derivatives object of this invention, may be easily prepared by reacting allyl esters of halogenoacetic acids with carbonyl or olefinic derivatives of nickel. Reactants may be used in proportions either stoichiometrical or not. The stoichiometry corresponds to l nickel atom (in the form of nickel derivative) per molecule of ester.

The allyl halogenoacetates as used comply with the general formula (II) wherein X, R R R R and R have the same meaning as above.

As allylic esters, there can be used, for example, allyl trifluoroacetate, crotyl difluoroacetate, methallyl monofluoroacetate, allyl trichloroacetate, allyl dichloroacetate, allyl difluoro-monochloroacetate, cinnamyl trifluoroacetate, l-octenyl 3-trifluoroacetate, 2- octenyl 4-trifluoroacetate, pinenyl-trichloroacetate, etc.

There can be used, for instance, the following nickel derivatives nickel tetracarbonyl, nickel bis-cyclopentadiene, nickel bis( 1,5 -cyclooctadiene), l, 5, 9 centronickel trans, trans, trans cyclododecatriene, nickel bis (3,7 dimethyl-l,5 cyclooctadiene), nickel cyclooctatetraene, nickel trisbicycloheptene, nickel bis-duroquinone etc. i The reaction according to this invention may be carried out either in the presence of an inert solvent, or without any solvent when the allyl ester is liquid. As solvents, there can be used ethers or saturated, aromatic or halogenated aromatic hydrocarbons.

The reaction is advantageously conducted at temperature of from to +l 20C and preferably within the range of from 20C to +60C. The process must be carried out in the absence of air, i.e. under an inert gas atmosphere, for instance argon, since the prepared compounds are sensitive to the action of air. The process according to the invention results in the direct obtainment with a substantially quantitative yield, of

pure products which can be used for initiating the stereospeciflc polymerization of compounds having ethylenic bonds without requiring any purification treatment.

The polymerizable monomers according to this invention, added as such or as mixtures, are compounds with ethylenic bonds and more particularly conjugated diolefins, preferably linear and containing from four to seven carbon atoms; there are for instance to be mentioned isoprene, piperylene, dimethylbutadiene and more particularly butadiene.

The proportion of catalyst, which may be extremely low, is chosen in consideration of the desired polymerization rate and molecular weight of the polymer. In most cases, there will be used at least 0.001 nickel atom (in the form of a complex thereof) and preferably from 0.1 to 2 nickel atoms per moles of the monomer. These preferred proportions are those for which there is obtained a polymer exhibiting the best properties as synthetic elastomer. The solvents optionally used in the polymerization reaction are advantageously selected from the group of the inert hydrocarbons, particularly paraffinic or cycloparaffinic hydrocarbons and their halogenated derivatives, more particularly their chlorinated derivatives. However there are preferred non-polar solvents such as paraffinic or cycloparaffmic hydrocarbons, which provide for a higher selectivity in cis-l ,4 units, whereas the polar solvents favor the formation of trans-1,4 units.

As examples of solvents preferably used for the formation of polybutadienes with a high content of cis-l ,4 units, are to be mentioned pentane, hexane, n-heptane, octane, isoheptane, iso-octane, cyclohexane and methylcyclohexane.

The polymerization reaction may be carried out at a pressure sufficient to maintain the reaction mixture substantially in the liquid phase. The pressure depends on the particular diluent optionally used and on the temperature at which polymerization is achieved, which temperature can be comprised between -4O and +120C and preferably between and +30C.

The process according to the invention can be carried out either as a continuous or as a batch process, by introducing the olefm(s) into a reactor containing the initiator and the diluent.

According to another embodiment of the invention, the catalytic species can be preformed by reacting the nickel compound with the allyl ester into the polymerization reactor and thereafter, without separating the resulting reaction product, the polymerization can be effected by adding the monomer.

It is however preferable first to eliminate the solvent when the same is an aromatic hydrocarbon and it is desired to obtain highly cis-l ,4 polymers.

According to a second embodiment, there is admixed in any order the nickel derivative, the allylic ester and the monomer .and polymerization is effected. In such a case it is preferred not to use a solvent of the aromatic type (aromatic hydrocarbon for instance) in order to obtain highly cis-1,4 polymers.

When the polymerization is complete, in the case of a batch process, the totalreaction mixture is subjected to a treatment for deactivating the catalyst and recovering the polymer. 7

Any convenient process may be used for this treatment of the reaction mixture.

According to one of said processes the polymer is recovered by distillation with steam of the diluent. In another convenient process there is added to the mixture a substance which deactivates the catalyst and precipitates the polymer, such as an alcohol. The polymer is thereafter separated from the precipitant and the diluent by means of any suitable method such as decantation or filtration. It is often preferred to add initially just the amount of substance which is necessary to deactivate the catalyst without causing the polymer to precipitate.

It has also been observed that it is advantageous to add an antioxidant agent, for example N-phenyl )8 naphthylamine or ditertiobutyl-paracresol to the solution of polymer, prior to recovering the latter. After addition of the substance for deactivating the catalyst and of the anti-oxydant agent, the polymer contained in the solution may be separated by adding an excess of a substance such as ethyl or isopropyl alcohol.

Besides, it is advantageous to add to the alcohol, during the precipitation of the polymer, a complexing agent for the metals of the catalytic system, such as acetylacetone or the disodium salt of tetracetic ethylene-diamino acid, which results in the easy obtainment of a polymer free from any metal residue.

It must be understood that other suitable means for recovering the polymer from the solution can be used according to the present invention. After having separated the polymer from the alcohol and the diluent by means of a filtration and other convenient operations, the polymer is dried.

The polymers obtained according to the invention are generally in a solid state, although there can be obtained a wide range of molecular weights from the liquid to the solid state. Besides, the cis-l,4 polybutadienes obtained according to the invention exhibit a series of properties(high molecular weights of narrow dispersion, low gel content, high unsaturation) which make them convenient for use as synthetic rubber.

The microstructure of the polybutadienes has been determined by infra-red spectrophotometryaccording to the method of D. MORERO, A. SANTAMBROGIO, L. PORRI and F. CIAMPELLI (La Chimica e lIndustria XLl-8-1959).

The following non-limitaive examples are illustrative of different embodiments of the invention, examples 4A and 9A are given by way of comparison only and are no part of the invention.

EXAMPLE 1 To a solution of 27.5 g of nickel bis-cyclooctadiene in cc of toluene, is added, under argon atmosphere, while stirring at 0C, a solution of 30g of allyl trifluoroacetate in 100cc of toluene. After 1 hour of reaction at 0C, the reaction mixture is evaporated under reduced pressure until obtainment of a dry solid. This residual solid is washed twice with 20cc of benzene and then dried under vacuum at the ambient temperature. There are obtained 18g of a yellow colored powder stable at the ambient temperature under argon atmosphere for several weeks.

The elementary analysis of this powder shows the respective contents of 28.1 percent of'carbon, 2.3 percent of hydrogen, 27.2 percent of nickel, 26.7 percent of fluor and 15.7 percent of oxygen, which corresponds to the raw formula C -,H NiOOCCF (theoretical composition :28,3 percent of carbon, 2.3 percent of hydrogen, 27.3 percent of nickel, 27 percent of fluor and 15.1 percent of oxygen) EXAMPLE 1A g of butadiene are added to the reaction product according to example 1. After stirring at 55C for'2 hours, there are obtained 60g of polybutadiene of the following structure 95 percent of cis-l,4 units, 4 percent of trans-1,4 units and 1% of 1,2 units and whose intrinsic viscosity, measured at 30C in toluene, is equal to 0.85 dl/g.

EXAMPLE 1B EXAMPLE 1c 52g of butadiene and 100cc of normal heptane are added to 1.5g of the reaction product according to example l. After stirring at 0C for 24 hours there are obtained 40g of polybutadiene whose micro-structure is composed of 96 percent of cis-1,4 units, 3 percent of trans-1,4 units and 1% of vinyl units.

EXAMPLE 1D 182g of butadiene and 200cc of normal heptane are added to 1.5g of the reaction product according to example 1. After stirring at 20C for 24 hours, there are obtained 165g of cis-1,4 polybutadiene having an intrinsic viscosity of 2 dl/g.

EXAMPLE 1E 61g of isoprene are added to 1.5g of the reaction product according to example 1. After stirring at 55C for 24 hours, there are obtained 15g of polyisoprene essentially composed of 1,4 units.

EXAMPLE 2 A solution of 15g of allyl trifluoroacetate into 100cc of normal heptane is added dropwise, at -C to a suspension of 27.5g of nickel bis-cyclooctadiene into 100cc of normal heptane. After stirring for 2 hours at 0C the so-formed precipitate is filtered, washed with normal heptane and dried under vacuum at the ambient temperature. There are thus obtained 24g of a powder whose elementary analysis corresponds to the formula C H NiOOCCF and exhibiting the same catalytic properties for stereospecific polymerization as those of the product according to example 1.

EXAMPLE 3 g of allyl trifluoroacetate are added to a solution of g of nickel tetracarbonyle into 100cc of benzene. After stirring at 50C for 3 hours, the reaction mixture is evaporated under reduced pressure until obtainment of a dry solid. The residue, after washing with benzene and drying under vacuum, finally gives 6g of a powder having a catalytic activity similar to that of example 1.

EXAMPLE 4 To a suspension of 14g of nickel bis-cyclooctadiene into 10000 of diethyl ether, is added, at 20C, a solution of 7.7g of allyl trifluoroacetate into 100cc of diethyl ether. After stirring at 0C for 1 hour, the reaction solution is concentrated under reduced pressure and then cooled down .to 70C. There can be separated, by filtration,'8.8g of powder. When, to 1.5g of said powder, are added 52g of butadiene and 200cc of isooctane, there are obtained, after stirring for 5 hours at 30C, 44g of polybutadiene containing more than 98% of cis-1,4 units andwhose intrinsic viscosity at 30C in toluene is equal to 2.6 dl/g.

EXAMPLE 4A By way of comparison example 4 is repeated except that allyl trifluoroacetate has been replaced by allyl chloride in the same proportion. There are recovered 8g of solid compound, unstable at the ordinary temperature. Polymerization of butadiene under the same conditions as described in example 4 is carried out with this compound and, after hours of reaction at 30C, there are obtained 3g of polybutadiene, containing 89 percent of cis-l ,4 units, 7 percent of trans-1,4 units and 4 percent of 1,2 units and exhibiting an intrinsic viscosity, measured at 30C in toluene, equal to 0.32 dl/g.

EXAMPLE 5 At 20C there are added 20cc of a solution of 15g of allyl trifluoroacetate per liter of normal heptane, to 0.5g of nickel bis-cyclooctadiene. After stirring for 30 minutes, the reaction mixture is evaporated under reduced pressure at ambient temperature until obtainment of a dry solid residue to which are thereafter added 2000 of normal heptane and 10.4g of butadiene. After stirring for 3 hours at the ambient temperature, there are obtained 8g of polybutadiene containing 94 percent of cis-l ,4 units, 5 percent of trans-1,4 units and 1% of 1,2 units.

EXAMPLE 6 To 0.5g of nickel bis-cyclooctadiene are added 20cc of a solution of 15g of allyl trifluoroacetate per liter of normal heptane and 10.4g of butadiene. After stirring for 20 hours at the ambient temperature, there are obtained 2.5g of polybutadiene, containing 86 percent of cis-l,4 units, 12 percent of trans-1,4 units and 2 percent of 1,2 units.

EXAMPLE 7 The mixture of a solution of 19g of nickel biscyclopentadiene into cc of toluene with a solution of 15.5g of allyl trifluoroacetate into 100cc of toluene is stirred for 3 hours at 60C. The reaction mixture is then evaporated under reduced pressure until obtainment of a dry solid which is washed twice with 20cc of benzene and dried under vacuum at the ambient temperature.

To 1.5g of the reaction product are added 52g of butadiene and 100cc of normal heptane. After stirring at 55C for 24 hours, there are obtained 34g of polybutadiene containing 98 percent of cis-1,4 units, 1 percent of trans-l ,4 units and 1% of vinyl units.

EXAMPLE 8 To a suspension of 27.5g of nickel bis-cyclooctadiene into 100cc of toluene, is added, at -20C, a solution of 41g of allyl trichloroacetate into 100cc of toluene. The mixture is stirred at 0C for 2 hours and then evaporated under reduced pressure at the ambient temperature, until obtainment of a dry solid.

To 1.5g of the reaction product are added 52g of butadiene and 100cc of normal heptane and the mixture is stirred at 0C for 20 hours.

There are thus obtained 28g of polybutadiene containing 96 percent of cis-1,4 units, 3.5 percent of trans- 1,4 units and 0.5% of 1,2 units.

EXAMPLES 9 12 To a suspension of 14g of nickel bis-cyclooctadiene into 100cc of normal heptane are added, according to each example, under stirring at 0C, such an amount of allyl ester that the molar ratio (nickel derivative/ester) be equal to 0.7. The temperature is thereafter allowed to raise up to 20C and, after stirring for 1 hour, the supernatant phase is decanted and the residual solid is washed successively four times with 50cc of normal heptane and thereafter, dried under reduced pressure up to maintenance of a constant weight.

The so-obtained 1r -allyl nickel halogenoacetate derivatives have been used for polymerizing butadiene under the following conditions solvent used normal heptane butadiene concentration in heptane 5.3 moles per liter concentration of the 1r -allyl nickel halogenoacetate in the reaction medium expressed in gram-atoms of nickel per liter 1 2.2.10

polymerization temperature 30C duration of the polymerization 5 hours.

The results obtained for each syntheses of 1r -allyl nickel halogenoacetate derivative and for each polymerization are summarized in the following table 2 Conversion Intrinsic rate to viscosity nickel Conversion measured vr-allyl rate to at 30 C. acetate or cis-1,4 in soluhalogeno polybutation in Ester used as acetate, dienc, toluene, Example reactant percent percent dl./g.

9 C H OOCCH2C1 90 3 0. 44

CCH; 80 0 CaH5OOCCHCl 92 19 0. 89 031150006013 92 40 2. 04 95 97 3. 32

According to the following examples, for which the same operating conditions as in examples 1 to 9 were used, has been carried out the syntheses of catalysts whose properties are similar to those of the previously manufactured catalysts. The following reactants have been used.

EXAMPLE13 '1, 5, 9-centro-nickel trans, trans, trans cyclododecatriene allyl difluoroacetate. 40

EXAMPLE14 Nickel bis-cyclooctadiene allyl monofluoro, dichloroacetate.

EXAMPLEIS Nickel cyclooctatetraene allyl dichloroacetate.

EXAMPLE 16 Nickel bis (3,7 dimethyl l,5-cyclooctadiene) methallyl monofluoroacetate.

EXAMPLE 17 Nickel bis-duroquinone pinenyl trichloroacetate.

What is claimed as this invention is:

l. A process for stereospecific polymerization of conjugated diolefins which comprises contacting at least one conjugated diolefin with a catalyst consisting essentially of the reaction product obtained from the reaction of an allyl halogenoacetate having the general formula:

wherein X is a halogen; n is an integer from 1 to 3; R R R R and R are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl, and aryl, the resulting allyl group containing from three to nine carbon atoms; or at least two of R R R and R are combined in a cyclic system containing from five to 12 carbon atoms with nickel carbonyl or nickel olefinic complex selected from the group consisting of nickel tetracarbonyl, nickel bis-cyclopentadiene, nickel bis (1,5-cyclooctadiene), 1,5,9 centro-nickel trans, trans, trans-cyclododecatriene, nickel bis (3,7 dimethyl-l, 5 cyclooctadiene), nickel cyclooctatetraene, nickel trisbicycloheptene and nickel bis-duroquinone at a temperature of from 40 to 120C.

2. The polymerization process according to claim 1 wherein the polymerization is carried out in an inert solvent selected from the group consisting of hydrocarbons and halogenated hydrocarbons.

3. The polymerization process according to claim 1 wherein the polymerization is carried out in aparaffinic hydrocarbon.

4. The polymerization process according to claim 1 wherein nickel is present in an amount of from 0.1 to 2 atoms per moles of the monomer.

5. The polymerization process according to claim 1, wherein the catalyst is contacted at a temperature of from -40 to +C.

6. The polymerization process according to claim 1, wherein the catalyst is contacted at a temperature between 0 and 30C.

7. The polymerization process according to claim 1, wherein the conjugated diolefin is a linear conjugated diolefin containing from four to seven carbon atoms in the molecule.

8. The polymerization process according to claim 1, wherein the diolefin is butadiene.

9. The polymerization process according to claim 1, wherein the catalyst is manufactured directly within a polymerization medium by reacting the allyl halogenoacetate with the nickel carbonyl or olefinic complex.

10. The polymerization process according to claim 1, wherein the reaction of the allyl halogenoacetate with nickel carbonyl or nickel olefinic complexes is effected at a temperature between -20C. and +60C.

1 1. The polymerization process according to claim 1, wherein the allyl halogenoacetate is selected from the group consisting of allyl trifluoroacetate, crotyl difluoroacetate, methallyl monofluoroacetate, allyl trichloroacetate, allyl dichloroacetate, allyl difluoromonochloroacetate, cinnamyl trifluoroacetate, l-octenyl 4-trifluoroacetate, and pinenyl-trichloroacetate. 

1. A process for stereospecific polymerization of conjugated diolefins which comprises contacting at least one conjugated diolefin with a catalyst consisting essentially of the reaction product obtained from the reaction of an allyl halogenoacetate having the general formula:
 2. The polymerization process according to claim 1 wherein the polymerization is carried out in an inert solvent selected from the group consisting of hydrocarbons and halogenated hydrocarbons.
 3. The polymerization process according to claim 1 wherein the polymerization is carried out in a paraffinic hydrocarbon.
 4. The polymerization process according to claim 1 wherein nickel is present in an amount of from 0.1 to 2 atoms per 100 moles of the monomer.
 5. The polymerization process According to claim 1, wherein the catalyst is contacted at a temperature of from -40* to +120*C.
 6. The polymerization process according to claim 1, wherein the catalyst is contacted at a temperature between 0* and 30*C.
 7. The polymerization process according to claim 1, wherein the conjugated diolefin is a linear conjugated diolefin containing from four to seven carbon atoms in the molecule.
 8. The polymerization process according to claim 1, wherein the diolefin is butadiene.
 9. The polymerization process according to claim 1, wherein the catalyst is manufactured directly within a polymerization medium by reacting the allyl halogenoacetate with the nickel carbonyl or olefinic complex.
 10. The polymerization process according to claim 1, wherein the reaction of the allyl halogenoacetate with nickel carbonyl or nickel olefinic complexes is effected at a temperature between -20*C. and +60*C. 